Characterization of complex photosynthetic pigment profiles in European deciduous tree leaves by sequential extraction and reversed-phase high-performance liquid chromatography

Leaf pigments, including chlorophylls and carotenoids, are important biochemical indicators of plant photosynthesis and photoprotection. In this study, we developed, optimized, and validated a sequential extraction and liquid chromatography-diode array detection method allowing for the simultaneous quantification of the main photosynthetic pigments, including chlorophyll a, chlorophyll b, β-carotene, lutein, neoxanthin, and the xanthophyll cycle (VAZ), as well as the characterization of plant pigment derivatives. Chromatographic separation was accomplished with the newest generation of core–shell columns revealing numerous pigment derivatives. The sequential extraction allowed for a better recovery of the main pigments (+25 % chlorophyll a, +30 % chlorophyll b, +42 % β-carotene, and 61% xanthophylls), and the characterization of ca. 5.3 times more pigment derivatives (i.e., up to 62 chlorophyll and carotenoid derivatives including isomers) than with a single-step extraction. A broad working range of concentrations (300–2,000 ng.mL$^{−1}$) was achieved for most pigments and their derivatives and the limit of detection was as low as a few nanograms per milliliter. The method also showed adequate trueness (RSD < 1%) and intermediate precision (RSD < 5%). The method was developed and validated with spinach leaves and their extracts. The method was successfully performed on leaf pigment extracts of European deciduous tree species. Within a case study using Fagus sylvatica L. leaves, pigment derivatives revealed a high within-individual tree variability throughout the growing season that could not be detected using the main photosynthetic pigments alone, eventually showing that the method allowed for the monitoring of pigment dynamics at unprecedented detail

Severe drought-influenced composition and δ ¹³C of plant and soil n- alkanes in model temperate grassland and heathland ecosystems

Drought events are predicted to increase under future climate change. In temperate ecosystems, plants are capable of resisting drought due to their hydrophobic wax layer, in which n-alkanes are important constituents. In soils, plant-derived n-alkanes are comparatively resistant to degradation. To improve understanding of the significance of n-alkanes in plant-soil systems during a severe drought period (104 days), we investigated bulk organic carbon (Corg) concentration, total lipid extract (TLE) concentration, n-alkane molecular ratios such as average chain length (ACL), carbon preference index (CPI) and chain length ratios of different n-alkane compounds, in addition to the compound-specific isotope composition (δ13C) of n-alkanes in model temperate grassland and heathland plant-soil systems. Although plant communities of two (heathland) and four (grassland) species were available, only one representative species per biome was accessible for the current study. Heathland plants and soil revealed significantly higher concentrations of Corg and TLE compared with grassland. TLE and alkane composition responded quickly during the first drought phase (0 – 40 days). This indicates that plants were actively utilizing C and produced more n-alkanes in order to withstand drought, which was confirmed by increased (2 – 3‰) δ13C values for n-alkanes in shoot biomass. However, during later drought phases all the parameters remained constant for plants and soils. This suggests limited change in biosynthesis and cycling of plant lipids such as n-alkanes during intense drought. Surprisingly, during the first drought phase, increased ACL and CPI ratios in soil demonstrated a rapid input of plant-derived long chain n-alkanes to soil, which was not expected due to the decadal residence time of alkanes in soil. The study enabled tracing of plant metabolic response in terms of alkane biosynthesis under different phases of drought and rapid cycling of alkanes in the plant-soil system

High-resolution record of stable isotopes in soil carbonates reveals environmental dynamics in an arid region (central Iran) during the last 32 ka

Although central Iran is pivotal for palaeoclimatic correlations, palaeoenvironmental data for this region is very sparse and a reliable chronology for pedogenic features is lacking. We therefore tried to answer the question how the environmental conditions and, in particular, the climate developed over time by using the isotopic signatures of pedogenic carbonates. We present a chronology of pedogenic carbonates in association with stable carbon and oxygen isotopes in both the matrix and coating carbonates of a relict palаeosol (Baharan palaeosol) in central Iran to understand the dynamics of environmental changes in this region during the late Quaternary. The palаeosol experienced several episodes of leaching during pedogenesis as reflected in its morphology (carbonate coatings under the rock fractions) and geochemical characteristics (Ba/Sr ratios). The δ$^{18}$O values of both the matrix and coating carbonates in the upper 60 cm (especially in the upper 20 cm) of the pedon are enriched (∼4‰) compared to the subsoil and are mainly related to the impact of evaporation. Moreover, the δ$^{13}$C values of the carbonates are in isotopic disequilibrium with the modern vegetation cover (desert shrubs) of the study area and are enriched in different degrees. The carbonates in the top 60 cm are formed by the input of atmospheric CO$_{2}$ and calcareous dust while deeper carbonates formed in an environment exhibiting a higher contribution of C$_{4}$ plants. Based on the radiocarbon chronology of carbonate coatings, it seems that three main stages of palaeoenvironmental changes occurred in the region during the last 32 ka. The first stage lasted ca. 5,000 years (between 31.6 and 26.0 ka) and was accompanied by deep leaching under sub-humid climatic conditions and the expansion of C$_{4}$ plants. Under the dominance of semi-arid conditions during the second stage until the late Holocene, a gradual increase in the δ$^{18}$O values and aridity occurred in the region. The last phase in the late Holocene was characterised by the establishment of an arid and evaporative environment with a sparse vegetation cover. A climatic correlation using the oxygen isotopic composition of secondary carbonates from the Baharan palaeosol, Soreq Cave (the Levant) and Hoti Cave (Oman; both having speleothems records) suggested a climatic connection between central Iran and the eastern Mediterranean during the late Pleistocene and between central Iran and northern Oman during the late Holocene

Warming and elevated CO2 promote rapid incorporation and degradation of plant-derived organic matter in an ombrotrophic peatland

Rising temperatures have the potential to directly affect carbon cycling in peatlands by enhancing organic matter (OM) decomposition, contributing to the release of CO2 and CH4 to the atmosphere. In turn, increasing atmospheric CO2 concentration may stimulate photosynthesis, potentially increasing plant litter inputs belowground and transferring carbon from the atmosphere into terrestrial ecosystems. Key questions remain about the magnitude and rate of these interacting and opposing environmental change drivers. Here, we assess the incorporation and degradation of plant- and microbe-derived OM in an ombrotrophic peatland after 4 years of whole-ecosystem warming (+0, +2.25, +4.5, +6.75 and +9°C) and two years of elevated CO2 manipulation (500 ppm above ambient). We show that OM molecular composition was substantially altered in the aerobic acrotelm, highlighting the sensitivity of acrotelm carbon to rising temperatures and atmospheric CO2 concentration. While warming accelerated OM decomposition under ambient CO2, new carbon incorporation into peat increased in warming × elevated CO2 treatments for both plant- and microbe-derived OM. Using the isotopic signature of the applied CO2 enrichment as a label for recently photosynthesized OM, our data demonstrate that new plant inputs have been rapidly incorporated into peat carbon. Our results suggest that under current hydrological conditions, rising temperatures and atmospheric CO2 levels will likely offset each other in boreal peatlands

Pedogenesis and carbon sequestration in transformed agricultural soils of Sicily

The increasing atmospheric CO2 concentration is a consequence of human activities leading to severe environmental deteriorations. Techniques are thus needed to sequester and reduce atmospheric carbon. One of the proposed techniques is the transformation or construction of new soils into which more organic carbon can be sequestered and CO2 be consumed by increased weathering. By using a chronosequence of new and transformed soils on crushed limestone (0–48 years) in a Mediterranean area (Sicily), we tried to quantify the amount of organic carbon that could be additionally sequestered and to derive the corresponding rates. A further aim was to trace chemical weathering and related CO2 consumption and the evolution of macropores that are relevant for water infiltration and plant nutrition. Owing to the irrigation of the table grape cultivation, the transformed soils developed fast. After about 48 years, the organic C stocks were near 12 kg m−2. The average org. C sequestration rates varied between 68 and 288 g m−2 yr−1. The C accumulation rates in the transformed soils are very high at the beginning and tend to decrease over (modelled) longer time scales. Over these 48 years, a substantial amount of carbonate was leached and reprecipitated as secondary carbonates. The proportion of secondary carbonates on the total inorganic carbon was up to 50%. Main mineralogical changes included the formation of interstratified clay minerals, the decrease of mica and increase of chloritic components as well as goethite. The atmospheric CO2 consumption due to silicate weathering was in the range of about 44–72 g C m−2 yr−1. Due to the high variability, the contribution of chemical weathering to CO2 consumption represents only an estimate. When summing up organic C sequestration and CO2 consumption by silicate weathering, rates in the order of 110–360 g C m−2 yr−1 are obtained. These are very high values. We estimated that high sequestration and CO2 consumption rates are maintained for about 50–100 years after soil transformation. The macropore volume decreased over the observed time span to half (from roughly 10 to 5 %). The transformation of soils may even amend their characteristics and increase agricultural production. Due to the relatively sandy character, enough macropores were present and no substantial compaction of the soils occurred. However, great caution has to be taken as such measures can trigger deterioration of both soil ecosystem services and soil quality

Whole-soil warming decreases abundance and modifies the community structure of microorganisms in the subsoil but not in surface soil

The microbial community composition in subsoils remains understudied, and it is largely unknown whether subsoil microorganisms show a similar response to global warming as microorganisms at the soil surface do. Since microorganisms are the key drivers of soil organic carbon decomposition, this knowledge gap causes uncertainty in the predictions of future carbon cycling in the subsoil carbon pool (> 50 % of the soil organic carbon stocks are below 30 cm soil depth). In the Blodgett Forest field warming experiment (California, USA) we investigated how +4 ∘C warming in the whole-soil profile to 100 cm soil depth for 4.5 years has affected the abundance and community structure of microorganisms. We used proxies for bulk microbial biomass carbon (MBC) and functional microbial groups based on lipid biomarkers, such as phospholipid fatty acids (PLFAs) and branched glycerol dialkyl glycerol tetraethers (brGDGTs). With depth, the microbial biomass decreased and the community composition changed. Our results show that the concentration of PLFAs decreased with warming in the subsoil (below 30 cm) by 28 % but was not affected in the topsoil. Phospholipid fatty acid concentrations changed in concert with soil organic carbon. The microbial community response to warming was depth dependent. The relative abundance of Actinobacteria increased in warmed subsoil, and Gram+ bacteria in subsoils adapted their cell membrane structure to warming-induced stress, as indicated by the ratio of anteiso to iso branched PLFAs. Our results show for the first time that subsoil microorganisms can be more affected by warming compared to topsoil microorganisms. These microbial responses could be explained by the observed decrease in subsoil organic carbon concentrations in the warmed plots. A decrease in microbial abundance in warmed subsoils might reduce the magnitude of the respiration response over time. The shift in the subsoil microbial community towards more Actinobacteria might disproportionately enhance the degradation of previously stable subsoil carbon, as this group is able to metabolize complex carbon sources

Two possible source regions for Central Greenland last glacial dust

Dust in Greenland ice cores is used to reconstruct the activity of dust-emitting regions and atmospheric circulation. However, the source of dust material to Greenland over the last glacial period is the subject of considerable uncertainty. Here we use new clay mineral and <10 µm Sr–Nd isotopic data from a range of Northern Hemisphere loess deposits in possible source regions alongside existing isotopic data to show that these methods cannot discriminate between two competing hypothetical origins for Greenland dust: an East Asian and/or central European source. In contrast, Hf isotopes (<10 µm fraction) of loess samples show considerable differences between the potential source regions. We attribute this to a first-order clay mineralogy dependence of Hf isotopic signatures in the finest silt/clay fractions, due to absence of zircons. As zircons would also be absent in Greenland dust, this provides a new way to discriminate between hypotheses for Greenland dust sources